Fabrics and other material and their manufacture



Dec. 21, 1937. ROBERTS 2,102,648

FABRICS AND OTHER MATERiTALlS AND THEIR MANUFACTURE Filed April 12, 1953 INVENTOR.

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B Y Y Q, WW 3' W ATTORNEYS.

FABRICS AND @THER MATERIAL A THEIR FAC'IURE Robert Pierce Roberts, Spondon, near Derby, England, assignor to Celanese Corporation of- America, a corporation oi Delaware Application April 12, 1933, Serial No. 665,630

x In Great Britain April 27, 1932 13 illaims.

This invention relates to improved fabrics and other materials and processes for their manufacture, and is. more particularly concerned with improved processes for the manufacture of filaments, yarns, threads, cords, ribbons, knitted, woven or other fabrics or other materials made of or containing cellulose acetate or other cellulose esters differentially saponified.

We have found that filaments, yarns, or the like of cellulose acetate or other cellulose esters which have been subjected to diilerent tensions so as to produce diiierent permanent extensions in the said products exhibit a differential resistof different denier.

ance to saponificatio-n treatments, and the present invention utilizes this discovery to obtain fabrics or other materials containing esters of cellulose which have been saponified to different extents, including the case in which one or more of the different types of yarn is not saponified at all.

In order to produce the fabrics or other materials which can be difierentially saponified in accordance with the present invention, it is only necessary to weave, knit, twist or otherwise associate filaments or yarns of cellulose acetate or other cellulose esters which have been subjected to different tensions so as to produce different permanent extensions. The said tensions may be applied to the materials during any convenient stage of their manufacture, including the actual spinning of the filaments or yarns themselves. Thus a. completely set yarn may be subjected to strain so as to produce a permanent extension thereof, and it is found that the yarn so treated is more resistant to saponifying treatments than is the untreated yarn. Similarly applying a dif- -ferent draw-down to the filaments or yarns during their manufacture either by wet or dry spinning processes produces this differential resistance to saponification treatments. In this latter case of applying different draw-down to the yarn during its manufacture it will be appreciated that, other things being equal, the yarns having the different draw-down applied thereto will be This difference in the yarn may be removed if desired by applying other means adapted to correct the diilerence in denier. Thus, if it is desired to apply a drawdown of 1.5 based on the extrusion speed to one yarn, and to apply a draw-down of 2 based on the extrusion speed to the other yarn, and at the same time to produce a product of substantially the same denier in the two cases, then in the first case jet orifices which are smaller than in the second case may be used, or alternatively or in addition the spinning solution used may be more dilute in the first case than in the second. Thus, for instance, we may in one case use jet orifices having a diameter of .07 or .08 millimetre, and in the other case jet orifices having an internal diameter of .055 millimetre and apply diilerential draw-down so as to obtain products of substantially the same denier in the two cases. In general, a given stretch applied continuously with the production of the yarn has more eiiect on its resistance to saponification than when applied to a completely set yarn:

In accordance with the present invention a difierential strain may also be applied to the filaments or other products after their manufacture. Thus one set of filaments for incorporation in a fabric or other material may be the normal product, and another set may be subjected to a process of stretching beyond the elastic limit, whereby a permanent extension is produced. This stretching beyond the elastic limit may be applied to the filaments or other products in the dry state or when wetted with water or with a softening liquid, such as an aqueous or other solution of a solvent or swelling agent for the cellulose ester under treatment, for instance an aqueous or other solution of acetone, glycerine, formaldehyde, thiocyanates, chlorinated hydrocarbons, for instance methylene chloride, ethylene chloride, dichlorethylene, chloroform, tetrachlorethane and the like, and the ethers, cyclic or non-cyclic, or esters or etheresters of glycols, including both olefine and polyolefine glycols, and glycerine and other polyhydric alcohols, for example the mono-methyl and ethyl ethers of ethylene and diethylene glycols, dioxane and its homologues and substitution products, for instance. diethylene dioxide dicarbinol monoor ell-acetate, or the corresponding dlethylene dioxide. dicarbinol and other cyclic ethers, for instance methylene ethylene dioxide, mono-acetin, diacetin, glycol mono-acetate and methyl glycol mono-acetate.

e extent of the permanent extension applied to the filaments or other materials may vary within very wide limits and accordingly the difference in resistance to saponification of the resulting yarns may vary considerably. Thus, for instance, even if a permanent extension of only 6% be applied to the materials a pronounced difierence in resistance to saponification is produced, while still greater difierence is produced by applying to one set of filaments or yarns a permanent extension of 15-20%, up to 50 or 100% sets of yarns is at least based on their original length. Such a stretch may be applied to the materials during their travel from one point to another either continuously with their production or subsequently as described e. g. in British Patent No. 323,790. Again they may be stretched ,in the form of hanks or other packages, as described in U. S. Patent No. 1,709,470, or in stages as described in British Patent No. 370,430, or while in warp formation, in which connection reference is made to British Patent No. 370,430.

The difierentially strained filaments, yarns, or the like may be associatedin any desired manner. For instance, in a woven fabric, one \type of yarn may constitute the whole of the weft and another type the whole of the warp, or both types may be in the weft or warp or both. In addition other types of yarn, for instance of Viscose artificial silk or other cellulosic type of silk, or of cotton, wool, natural silk or cellulose ethers, may be incorporated in the fabric in any desired manner, and it will be appreciated that in accordance with the particular pattern in which the association takes place different effects may be produced in the fabric when the saponifying treatment is applied in accordance with the invention. The invention further includes the differential saponification of cords, knitted fabrics or any other materials containing two or more yarns of cellulose acetate or other cellulose esters which have different resistance to saponification due to difierential strain having been applied at some stage during the manufacture of the filaments or yarns.

In addition to exhibiting difierential resistance to saponification the diiferentially strained filaments, yarns and other materials used in the present invention exhibit a differential resistance to delustring, and accordingly efiects due to such difierential delustring may be superimposed upon the efiects due to difierential saponification. In general the filaments or yarns which exhibit least resistance to saponification exhibit least resistance to delustring. The delustring may be achieved by suitable modification of the saponitying treatment, since, as is known, saponlfying treatments may be applied under conditions such that the lustre is retained, or that the lustre is modified; or the delustring action of hot or boiling aqueous media or moist steam may be utilized' to obtain the differential lustre effect. Such differential delustring treatment may be applied either before, after or together with the dinerential saponifying treatment.

While in general, as is stated above, the materials which exhibit the least resistance to saponification also exhibit the least resistance to delustring, and therefore the constituents of the materials obtained according to the present invention which are most saponifiable will also be most delustrable, yet in certain circumstances saponification may be eflz'ected so that the more saponifled materials have the greater lustre. Thus, for example, when saponification is carried to the stage at which the cellulose ester material is substantially or completely saponified, the material may acquire a resistance to delustring and may even increase in lustre, so that a material containing a constituent which is substantially saponified and has a lustre greater than that of the remaining less saponified constituents may be obtained.

The invention as described above has been more particularly addressed to the case in which aioaeae the whole length of one set of filaments or yarns appearing in the fabric or other material has been subjected to a permanent extension different from that applied to the whole length of another set of filaments or yarns. A more important aspect of the present invention consists in applying different permanent extensions along the length of the filaments or yarns. Thus, for instance, at one point the yarn may be subjected to a permanent extension of 6, 10, 15, 20% up to 100% or even more of its length, and another portion of the length may be the normal yarn produced by the spinning apparatus, or alternatively at one point it may be stretched 10%, at another point 20% and so on. Means whereby such differentially strained yarns may be produced are described in U. S. Patent No. 2,004,139. Thus one such method which may be employed to produce intermittently strained threads consists of a pair of rollers round which the threads are caused to pass in turn, the second of such rollers rotating at a peripheral speed greater than the first. Such rollers would themselves stretch the threads in accordance with the differencein their peripheral speeds. Means may, however, be provided to vary at predetermined intervals and to predetermined extents the length of the path followed by the threads between the rollers, so that during increase of such length the stretching action of the second of the rollers is localized on the thread, the roller operating to stretch the thread between the rollers, and during lessening of the length the second roller is principally occupied in taking up the excess length of thread available.

A further roller or rollers having appropriately higher peripheral speeds may be aranged to follow the second roller, and further means for varying the path followed by the thread may be arranged between the further pair of rollers so provided. These further means may operate synchronously with the length varying means between the first pair of rollers, or may operate out of phase of such means so as to vary the incidence and amount of the strain falling upon the thread.

The path varying means may comprise a reciprocating, oscillating, or rotating member or members actuated at any desired regular or irregular rate of operation and serving to vary the path of the threads to any desired regular or irregular extent. For example, a bar may be reciprocated by a cam, eccentric, crank, or the like so that it engages a thread in its passage between a pair of rollers, the amplitude of movement of the bar determining the amount of strain imparted to the thread. Such device is convenient for the production of strained portions at fairly long intervals along the thread. For shorter intervals, say

2" apart, a rotating member may be used to deflect the thread from its direct path from roller to speed is carefully adjusted to feed the thread steadily onward, allowance being made for any slippage that may take place round either of the rollers. To reduce the possibility of slip, the thread may be taken more than once round each roller.

Intermittent stretching of the materials may be effected while they are in a dry state or wetted with water or any of the softening liquids mentioned above.

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The threads may receive an intermittent straining while they have little or no twist, or after they have been given a medium or high degree of twist. They may be used for the production of knitted, woven, or other fabrics or articles directly after .production, that is while they retain their original twisted or untwisted condition. In woven fabrics, a streaky or mottled effect may be produced, variations in the length and frequency of the strained portions, as well as in the degree of straining,

enabling correspondingly varying efiects to be mittent straining takes place at relatively short Further, the

intervals, such as A to inch. threads may be doubled, with any desired degree of twist, with other threads, which may also be intermittently strained.

The straining of yarns and threads, whether intermittent or continuous, is in general applied under such conditions that rupture of the individual filaments does not occur, but if desired it may be effected in such a manner that individual filaments are broken, while the continuity of the main filament bundle is maintained. In this way a yarn which resembles a spun yarn either throughout its length or intermittently may be obtained. Methods of carrying out this feature are described in U. S. Patent No. 2,098,980, to which reference is made broadly. The yarns or threads may consist wholly of cellulose ester materials, or may also contain natural or other arti-' ficial textiles.

The intermittent strain may be imparted continuously with the production of the filaments.

For example, the intermittent straining may be round stretching rollers of the type previously indicated, or through any other suitable apparatus, after emergence of the threads from the spin- The threads may then be collected with or without twisting, e. g. the threads may be collected by means of a cap-spinning device. Similar methods may be employed for intermittently straining the threads or mixed threads containing two or more types of continuous filaments (e. g. cellulose acetate filaments mixed with viscose filaments) or one or more kinds of continuous filaments together with other filaments or fibres, during bobbin-to-bobbin or other winding or twisting and winding operations. The continuous filaments in the threads may be of the same or different denier.

Doubling may be employed to produce composite threads some or all of the component threads of which have been intermittently strained. The doubling may be effected continuously with the intermittent straining operation or the composite threads may be produced in a separate doubling operation. For example, a composite artificial thread may be produced in a similar manner to the doubled thread of difierentially strained artificial filaments described in U. 8. Patent No. 1,976,201. Thus, one or more component threads may be intermittently strained and joined by an unstrained thread or threads at the ballmn guide of a cap-spinning be drawn down from the jet or from a package by a feed roller rotating at the same peripheral speed as the last roller engaged by the intermittently strained thread or threads, or this last roller may serve as the feed roller for the unstrained thread or threads. The several threads entering into the composition of the doubled thread may be produced from a single jet, the filaments of which are divided in accordance with the number of filaments desired in each thread, or from two or more jets in the same or in separate spinning cells and having any required number of spinning orifices to produce'filaments of any desired denier. The threads may be, if desired, collected by simple winding, and afterwards doubled to any degree of twist.

The yarns to which have been applied difierential permanent extensions along their length may constitutethe whole of the fabric or other material, or such yarns may be associated with any other yarns, for instance yarns other than those of cellulose esters, or may be associated with any of the yarns previously referred to which have uniform properties along their length.

Any suitable saponification treatment may be applied in accordance with the present invention, the only criterion being that the treatment shall not be sufliciently vigorous to mask the effects of differential resistance to saponification characteristic of the invention. It is, however, quite easy to choose the, conditions of the saponifying treatments so that very pronounced differences in saponification are produced on the different yarns. Most advantageously the saponifying treatment is chosen so that substantially no saponification takes place on one type of filament or yarn, while substantial saponification takes place on one or more other types. The saponification may be a simple bath treatment with an aqueous solution of a saponifying agent, as for instance caustic mda, caustic potash, trisodium phosphate or the like or the saponifying agent may be. applied in alcoholic medium, for instance in a medium of methyl or ethyl alcohol in accordance with British Patent No. 125,153, or in a medium of another alcohol or a glycol or glycerine or other polyhydric alcohol in accordance with the process of U. S. application S. No. 283,999 filed June heated drums. Again the saponifying agent, for

instance ammonia, may be applied in vapour form as described e. g. in US. Patents Nos. 1,895,919 and 1,895,929. Bufler salts, for instance sodium acetate, or soaps may be con 'tained in the saponifying liquors. The materials may also be locally saponified e. g. by printing with a suitable saponifying paste.

The invention has been described above more particularly in relation to the manufacture and treatment of fabrics or other materials made of or containing cellulose acetate. This cellulose acetate is more particularly the customary com-' mercial acetone-soluble cellulose acetate. It will be realized, however, that the invention is by no means limited to this compound, and it may be applied to the manufacture and treatment of fabrics or other materials made of or containing other cellulose acetates or other cellulose esters, for instance cellulose formate, cellulose propionate, cellulose butyrate, and so forth. It is not essential that the two types of yarn contained in one fabric or material should consist of the same cellulose ester, since the differential resistance to sa'ponification produced by differential straining and characteristic of the invention may be superimposed upon differential resistance to saponification due to other causes, as for example differences in the spinning conditions, differences in the acidyl value of the cellulose ester used, and differences in the nature of the ester group. These features are utilized to produce similar effects in U. S. application S. No. 482,280 filed September 16th, 1930.

The effects due to differential saponiflcation with or without differential delustring in accordance with the present invention may be utilized to produce colour effects by applying to the differentially saponified materials dyestuffs which have differential aifinities for the different types of material therein. Thus, for instance, the saponified yarn may be treated with cotton or other dyestuffs having an aflinity for cellulose, and shading may be produced in accordance with the degree of saponification. Unsaponified yarns or yarns of non-ester materials may be dyed or otherwise coloured with the appropriate dyes. For example, the aflinity of the insoluble type of colouring matter now customarily applied to cellulose ester materials in general decreases as the degree of saponification increases and thus by dyeing the materials obtained according to the present invention with such dyestuffs, products showing shaded effects may be obtained. Discharge effects may be obtained on the goods in accordance with the methods, known in the art, or the materials may be printed or otherwise coloured in any suitable manner.

Saponification and dyeing of the materials may if desired be carried out simultaneously in a single bath, in which case dyestuffs which are not affected by the saponifying agent should of course be employed.

The following examples illustrate the invention but it is to be clearly understood that they do not limit it in any way:-

Example 1 Gum arabic thickening 1:1 85 Water 40 Caustic soda 4 6 It is then passed over drying drums in order to dry the paste and steamed for 15 minutes at 5 lbs. pressure, and a material which is non-uniformly saponified is thus obtained.

Example 2 The following example shows the simultaneous saponification and dyeing of material. A mixed fabric having a warp of cotton, viscose or similar cellulosic type of yarn and a weft consisting of threads in which some of the filaments have been stretched e. g. by 50-100% of their original aioaeae length and some are the normal type of yarn,

obtained, for example, as described in U. S. Patent No. 1,976,201 is dyed in an aqueous bath containing .1% soap, .05% caustic soda and about 1% (on the weight of the material) of Chlorazoi sky blue. The volume of the bath is about times that of the fabric. The dyeing is carried out at about 80 C. until the desired differential colour effect is obtained, which in general requires 1 to 2 /2 hours.

Examples of materials which may be obtained according to the present invention are illustrated in the accompanying drawing but it is to be clearly understood that they are given merely by way of illustration and that the invention is in no way limited thereto:--

Figure 1 illustrates a differentially saponified fabric obtained by treating a material containing a-weft 5 of normal cellulose acetate yarn or cotton or regenerated cellulose or other yarn and a warp ii of a cellulose acetate yarrrwhich has been difierentially stretched along its length. a

Figure 2 represents a differentially saponified fabric obtained by treating a material in which the weft l is a normal yarn and the warp 6 is a cellulose acetate yarn which has been uniformly stretched.

Figure 3 shows a differentially saponified cord obtained by treating a cord containing normal threads 8 and cellulose acetate threads 9 which have been intermittently stretched.

What I claim and desire to secure by Letters Patent is:

1. Process for the production of materials particularly adapted for the production of color and other effects, which comprises subjecting materials containing organic esters of cellulose, different portions of which materials have been stretched to different extents, to saponification under such conditions that the portions which have been stretched to different extents are saponified to different extents.

2. Process for the production of materials particularly adapted for the production of color and other effects, which comprises subjecting materials containing cellulose acetate, diiferent portions of which materials have been stretched to different extents, to saponification under such conditions that the portions which have been stretched to different extents are saponified to different extents.

3. Process for the production of materials particularly adapted for the production of color and other effects, which comprises subjecting materials containing cellulose acetate, different portions of which materials have been stretched in fully formed condition to different extents, to saponification under such conditions that the portions which have been stretched to diiferent extents are saponified to different extents.

4. Process for the production of materials particularly adapted for the production of color and other effects, which comprises subjecting threads of organic esters of cellulose, which have been stretched in the fully formed condition along selected portions of their'lengths, to saponification under such conditions that the unstretched portions are saponified while the stretched portions are unsaponified.

5. Process for the production of materials exhibiting color effects, which comprises subjecting materials containing organic esters of cellulose, different portions of which materials have been stretched to different extents, to saponiflcation under such conditions that the portions which have been stretched to different extents are saponifiedto different extents, and simultaneously applying a coloring agent having difierent afiinities for saponified and unsaponified organic esters of cellulose, respectively.

6. Process for the production of materials particularly suitable for the production of color and other effects, which comprises stretching materials containing organic esters of cellulose so that diiferent portions are stretched to different extents, and then saponifying the materials under such conditions that the portions which have been stretched to different extents are saponified to diflerent extents.

7. Process for the production of materials particularly adapted for the production of color and other effects, which comprises stretching along selected portions of their length threads containing cellulose acetate, and then saponifying the threads under such conditions that the unstretched portions are saponified while the stretched portions are unsaponified.

8. Process for the production of materials particularly adapted for the production of color and other effects, which comprises stretching along selected portions of their length threads containing cellulose acetate and being in the fully formed condition, and then saponifying the threads under ent extents, then saponifying the materials undersuch conditions that the portions which have been stretched to different extents are saponified to difierent extents, and simultaneously applying a coloring agent having I different affinities for saponified and unsaponified organic esters of cellulose, respectively.

10. Materials comprising organic esters of cellulose, said materials having differentially strained portions saponified to different extents.

11. Materials comprising'cellulose acetate, said materials having differentially strained portions saponified to different extents.

12. Materials comprising organic esters of cel lulose, said materials having strained and unstrained portions, the unstrained portions being saponified.

13. Materials comprising cellulose acetate, said materials having strained and unstrained portions, the unstrained portions being saponified.

ROBERT PIERCE ROBERTS. 

